WO2006019190A1 - Method for producing electrophotographic photosensitive body for negative charging, electrophotographic photosensitive body for negative charging, and electrophotographic system employing it - Google Patents

Abstract

A method for producing an electrophotographic photosensitive body for negative charging capable of enhancing adhesion between first and second layers without lowering the effect of reducing image defect while reducing total cost, an electrophotographic photosensitive body for negative charging produced by that method, and an electrophotographic system. The method for producing an electrophotographic photosensitive body for negative charging is characterized in that a substrate having a first layer laid thereon is placed in a film deposition furnace while removing at least the head part of a protrusion, plasma processing is performed on the surface of the first layer with a dilution gas consisting of a gas containing at least a group XIII element on the periodic table and at least one element selected from hydrogen, argon and helium, and then a second layer of a non-single crystal material is deposited on the first layer. An electrophotographic photosensitive body for negative charging, and an electrophotographic system employing it are also provided.

Description

 Patent application title: METHOD FOR PRODUCING ELECTROPHOTOGRAPHIC PHOTOSENSITIVE ELECTRODE FOR NEGATIVELY CHARGED, AND ELECTROPHOTOGRAPHIC PHOTOSENSITIVE FOR NEGATIVELY CHARGED ELECTROGRAPH

Technical field '

 The present invention relates to a method for producing a negatively charged electrophotographic photosensitive member that has few image defects and can maintain good image formation for a long period of time, and a negatively charged electrophotographic photosensitive member, and an electrophotographic apparatus. .

Background art

 Materials that form the photoconductive layer in solid-state imaging devices or electrophotographic photoreceptors and document readers in the field of image formation have high sensitivity and a high SN ratio [photocurrent (Ip) / dark current (Id)]. It has absorption spectrum characteristics that match the spectral characteristics of the electromagnetic waves that it emits, has fast photoresponsiveness, has the desired dark resistance, is non-polluting to the human body during use, and in solid-state imaging devices However, characteristics such as the ability to easily process afterimages within a predetermined time are required. In the case of electrophotographic photoreceptors used in offices as office machines, the above-mentioned pollution-free property is an important point.

From this perspective

Among these materials, there is amorphous silicon (hereinafter referred to as “a-S ij”) in which dangling bonds are modified with monovalent elements such as hydrogen and halogen atoms. Has been applied.

Conventionally, as a forming method for forming an electrophotographic photosensitive member made of a-Si on a conductive substrate, a sputtering method and a method of decomposing a source gas by heat Many methods are known, such as (thermal CVD method), a method of decomposing source gas from light (photo CVD method), and a method of decomposing source gas by plasma (plasma CVD method). Among these, the plasma CVD method, that is, a method of forming a deposited film on a conductive substrate by decomposing a source gas by a glow discharge such as direct current, high frequency, or microwave is used in the field of formation methods of electrophotographic photoreceptors and the like. Currently, practical application is very advanced. As a layer structure of such a deposited film, in addition to a conventional electrophotographic photosensitive member in which a-Si is used as a matrix and appropriately modifying elements are added, it has a blocking ability on the surface side. In addition, a configuration in which a so-called upper blocking layer or surface protective layer is laminated has also been proposed (see, for example, JP-A-08-15882). In Japanese Patent Laid-Open No. 08-15882, a photosensitive layer is provided in which an upper blocking layer containing an atom for controlling the conductivity is provided between the photoconductive layer and the surface protective layer, the carbon atom content being reduced from that of the surface protective layer. The body is disclosed.

 In addition, a-Si films have the property that, when dust of the order of several μm adheres to the substrate surface, abnormal growth occurs with the dust as a nucleus during film formation, and protrusions grow. ing. This protrusion causes a defect on the image. In order to prevent this image defect, a technique for flattening the top of the protrusion on the surface of the photoreceptor after film formation by polishing has also been proposed (see, for example, JP-A-2001-318480). In Japanese Patent Laid-Open No. 2001-318480, an electrophotographic photosensitive member is held and rotated, and the polishing tape is fed while the polishing tape wound around an elastic roller and the surface of the photosensitive member are in pressure contact. And a post-processing method for flattening and polishing the protrusions on the surface of the photoconductor.

FIG. 1 shows an example of the protrusion. The protrusion (111) has a conical shape starting from the dust (110), and has a low resistance due to the large number of localized levels at the interface (112) between the normal deposit and the protrusion. The charged charge at the interface It has the property of passing through (1 12) to the substrate side. For this reason, the projected portion appears as a white point on the solid black image on the image (in the case of reversal development, it appears as a black dot on the solid white image). These so-called “pochi” image defects have not been treated as defective even if they existed on several A3 sheets depending on the size, but when they are installed in color copiers. A further quality improvement is required, A

Even if one sheet is present on three sheets, it may be defective. Since these protrusions start from the dust, the substrate to be used is precisely cleaned before film formation, and all the steps to install in the film formation apparatus are performed in a clean room or under vacuum. Efforts have been made to minimize the amount of dust adhering to the substrate before starting, and this has been effective.

However, the cause of the protrusion is not only the dust attached to the substrate. In other words, when an a-Si photoreceptor is manufactured, the film formation time is several hours to several tens of hours because the film thickness is very large, from several μπι to several tens of zm. During this time, the a-Si film is deposited not only on the substrate but also on the film forming furnace wall and the structure in the film forming furnace. The deposits deposited on these furnace walls and structures are not film-like deposits deposited on the substrate, but may be powdery deposits. In some cases, peeling occurred in the film. Even if a slight amount of peeling occurs during film formation, it becomes dust and adheres to the surface of the photoconductor during deposition. Protrusions, which are abnormally grown parts, are generated starting from this. Therefore, in order to maintain a high yield, polishing is performed to flatten abnormally grown protrusions, and an upper blocking layer having a blocking ability against charged charges is laminated so as to cover the flattened protrusions. However, it has been effective to prevent the phenomenon that the charged charges slip through the protrusions and the interface between the normal part and the protrusions (see, for example, JP-A-2004-133396). ' In addition, as a method for applying the a-Si photoconductor, a corona charging method using corona charging, a roller charging method in which charging is performed by direct discharge using a conductive roller, magnetic particles, etc. are used to provide a sufficient contact area. There is an injection charging method in which charging is performed by directly injecting charges onto the surface of the photoreceptor. Among them, since the corona charging method and roller charging method use discharge, discharge products are likely to adhere to the surface of the photoreceptor. In addition, a-Si photoconductors have a surface layer that is much harder than organic photoconductors, so that the discharge products are likely to remain on the surface, and are absorbed by moisture in high humidity environments. The discharge product and moisture combine to lower the resistance of the surface, and the charge on the surface can easily move, resulting in an image flow phenomenon. For this reason, various ideas such as the surface rubbing method and the temperature control method of the photosensitive member may be required.

 In contrast, the injection charging method does not actively use discharge, but directly injects charge from the part in contact with the surface of the photoconductor. Hateful. In addition, the contact charging method, which is a contact charging method, is a voltage control type, while the corona charging method is a current control type. . In the conventional injection charging method, the charging performance can be improved by bringing the contact charging member of magnetic brush-like particles made of a magnetic material and magnetic particles into contact with the surface of the photoreceptor (see, for example, Japanese Patent Application Laid-Open No. 08-6353). . Disclosure of the invention

 Such a conventional method for producing an electrophotographic photosensitive member makes it possible to obtain an electrophotographic photosensitive member having practical characteristics and uniformity to some extent.

However, the demand for image defects is becoming stricter year by year for higher image quality in color copiers, and higher-quality electrophotographic photoreceptors are desired. The

 In addition, as described above, the injection charging method has various advantages. For example, in the contact injection charging method using a magnetic brush charger, the magnetic brush directly rubs the surface of the photosensitive member, so that the upper blocking layer In addition, it is necessary to produce an electrophotographic photosensitive member having good adhesion with careful management of the method of creating the surface layer.

 Therefore, as in the past, if the photoconductor is placed in the film furnace again after performing planarization polishing of the protrusions, and the upper blocking layer is laminated as the second layer, the adhesion between the layers decreases. May occur. This problem is that when the protective layer and the upper blocking layer that are laminated for the purpose of preventing the photosensitive member from being scratched by the polishing process are layers made of a non-single-crystal material containing at least carbon and silicon, This is due to a layer structure in which an upper blocking layer having a relatively low carbon content is stacked after a protective layer having a relatively high carbon content is stacked. It is considered that the adhesiveness is lowered due to the relationship in which a layer having a low carbon content is laminated after such a layer having a high carbon content. In addition, after the upper blocking layer is laminated, it is necessary to further laminate a surface protective layer as a second layer in order to protect the surface of the photoreceptor, increasing the overall cost.

 In order not to provide a low-adhesion joint by laminating a layer with a relatively low carbon content after a layer with a relatively high carbon content in order to maintain adhesion, and not to increase the overall cost, There is a demand for a method of manufacturing a photoreceptor that can be laminated with a surface protective layer on the flattened protrusion without laminating an upper blocking layer and can have a blocking ability against charged charges.

As a result of intensive research to solve the above-mentioned problems, the present inventors have produced an electrophotographic photosensitive member for negative charging having a photoconductive layer made of a non-single crystal material as described below. What is the effect of reducing adhesion and image defects? Thus, the inventors have found that the photoreceptor can be produced stably and inexpensively without causing any adverse effects, and the present invention has been completed.

 Namely, an electrophotographic photosensitive member for negative charging including a layer made of a non-single crystal material

• As a first step in this manufacturing method, a cylindrical substrate having a conductive surface is installed in a vacuum-tight film-forming furnace connected to an evacuation means and equipped with a raw material gas supply means. And a base layer on which the first layer is laminated as a second step, and a step of depositing a photoconductive layer made of at least a non-single crystal material as the first layer on the substrate. A step of removing from the film forming furnace, a step of removing at least the top of the protrusion on the surface of the first layer laminated in the first step, as a third step; As the fourth step, the substrate after completion of the third step is placed in a vacuum-tight film-forming furnace equipped with exhaust means and source gas supply means, and at least one periodic table group 13 element is installed. Gas containing hydrogen and hydrogen, argon, A process of plasma-treating the surface of the first layer with a diluent gas selected from lithium; and as a fifth step, at least the source gas is decomposed by high-frequency power, and • on the first layer The present invention also relates to a method for producing a negatively charged electrophotographic photoreceptor, comprising a step of laminating a layer made of a non-single crystal material as a second layer.

In addition, it is preferable to form an upper blocking layer containing at least one group 13 element of the periodic table in the first layer in terms of improving electrical characteristics, and the upper blocking layer. It is more preferable from the viewpoint of suppression of potential unevenness that the composition ratio of carbon to silicon constituting is increased toward the surface side. The content of the Group 13 element in the periodic table with respect to the total number of constituent elements contained in the upper blocking layer is 100 atoms! ) In terms of electrical characteristics, it is desirable to form it so that it is pm or more and 30000 atoms pp m or less. That's right.

 In addition, it is preferable that a protective layer containing at least silicon is formed on the outermost surface of the first layer in terms of scratch resistance in the step of removing the top of the protrusion.

 Further, in the third step, it is preferable from the viewpoint of workability and uniformity that the step of removing at least the top of the protrusion on the surface of the first layer is a polishing process.

Further, the heating setting temperature of the substrate may be changed between the third step and the fourth step, and further, by performing a process of contacting with water between the third step and the fourth step. Then, the adhesion when the second layer is laminated is improved, and the latitude for film peeling is widened. Further, in the fourth step, the content of the Group 13 element in the periodic table in all the gases introduced is 2.0 X l (T ⁴ mol% or more, 2.0 X l (T ² mol% or less). B ₂ H 6 is more preferable in terms of handling as a gas containing Group 13 elements of the periodic table in the fourth step.

The present invention also provides a photoconductive layer made of at least a non-single crystal material, a top blocking layer made of a non-single crystal material containing carbon and silicon, and a protective layer on a cylindrical substrate having at least a conductive surface. And an abnormally grown portion in the first layer is a second layer formed by laminating a second layer made of at least a non-single crystal material on the first layer. The negatively charged electrophotographic photosensitive member is characterized in that the content distribution of the Group 13 element of the periodic table has a peak in the interface region between the first layer and the second layer. Further, it is more preferable from the viewpoint of potential unevenness that the composition ratio of carbon to silicon constituting the upper blocking layer increases toward the surface side of the photoreceptor. Further, the periphery in the interface region between the first layer and the second layer. It is preferable in terms of image defect reduction and electrical characteristics that the peak of the content distribution of the group 13 element in the period table is 5.0 × 10 ¹⁷ pieces / cm ³ or more and 1.0 × 10 ²¹ pieces / cm ³ or less.

 As described above, according to the method for producing a negatively charged electrophotographic photosensitive member of the present invention, an interface having a blocking ability against charged charges is formed on the protrusion surface from which the top of the head has been removed. By having the plasma processing step to be performed, it is not necessary to stack the upper blocking layer as the second layer, and the adhesion can be improved while maintaining the effect of reducing image defects. In addition, the film formation process has been simplified, and the overall cost has been reduced. In addition, potential unevenness could be suppressed by increasing the composition ratio of carbon to silicon constituting the upper blocking layer laminated as the first layer toward the surface side. Brief Description of Drawings

 FIG. 1 is a schematic cross-sectional view showing an example of a protrusion of an electrophotographic photosensitive member. FIG. 2 is a schematic cross-sectional view showing an example of the protrusion of the electrophotographic photosensitive member of the present invention after polishing the surface of the first layer.

 Fig. 3 is a schematic cross-sectional view showing the electrophotographic photosensitive member laminated up to the first layer used in the experimental example.

 FIG. 4 is a schematic cross section showing an example of a negatively charged electrophotographic photosensitive member of the present invention.

 FIG. 5 is a schematic cross-sectional view of an RF plasma C V D a-Si photoconductor film forming apparatus.

 FIG. 6 is a schematic cross-sectional view of the surface polishing apparatus used in the present invention.

 FIG. 7 is a schematic cross-sectional view of the water cleaning apparatus used in the present invention.

FIG. 8 is a schematic cross-sectional view showing an example of the electrophotographic apparatus of the present invention. FIG. 9 is a schematic diagram showing the content distribution of Group 13 element (boron atom) of the periodic table in the negatively charged electrophotographic photosensitive member of the present invention.

 l 0 is a schematic diagram showing a change in the composition ratio of carbon to silicon constituting the upper blocking layer of the present invention.

 ,

BEST MODE FOR CARRYING OUT THE INVENTION

 The present inventors have studied improvement of image defects caused by protrusions, which is an important problem in a photoreceptor made of a non-single crystal material, particularly an a-Si photoreceptor. In particular, efforts have been made to prevent image defects caused by protrusions caused by film peeling from structures in the reactor wall during the formation of the deposited film. ,

 Protrusions become image defects such as spots, because there are many localized levels at the protrusions that are abnormally grown, and at the interface between the protrusions and the normal deposition part of the deposited film. This is because the charged charges escape to the substrate side through the protrusions and the interface. However, since the protrusions generated by the dust attached during film formation grow not from the substrate but from the middle of the deposited film, if the surface side is covered with a part that has some blocking ability, Intrusion, and even if protrusions are present, they will not cause image defects. Specifically, as shown in FIG. 2, after the first layer (202) is stacked, the top portion of the protrusion (21 1) is removed and planarized, and then a portion having a blocking ability is formed. . .

Currently used is a method of laminating a layer containing an upper blocking layer and a surface protective layer as the second layer. However, although this method has an effect of reducing image defects, there is a problem in that the adhesiveness is lowered due to the relation that a layer having a low carbon content is laminated after a layer having a high carbon content. The purpose of protecting the photoconductor after laminating the upper blocking layer Therefore, the surface protective layer had to be further laminated, which increased the overall cost.

 Therefore, the present inventors have conducted intensive studies, and without forming an upper blocking layer as the second layer, an interface having a blocking ability against charged charges is formed between the first layer and the second layer. We have established a plasma processing method that can be formed, and found that it is effective to reduce image defects simply by laminating only the surface protective layer as the second layer. This is because the process of removing the top of the protrusion is applied to the protrusion, and the protrusion surface in a state where the photoconductive layer is exposed on the surface is modified by the plasma process to the order of several atoms. This is probably due to the fact that the interfacial surface has a stopping ability, preventing the charge from entering the protrusions.

 In this way, instead of the previous upper blocking layer (second layer), the upper blocking layer (second layer) can be stacked by forming an interface on the projection surface that has the ability to block charged charges. In addition, it is possible to prevent a decrease in adhesion due to, and to eliminate the necessity of laminating an upper blocking layer (second layer), thereby reducing the overall cost.

 In addition, the present inventors have made various electrophotographic processes and various photoconductor manufacturing conditions in order to achieve higher image quality and higher durability for the combination of an electrophotographic apparatus and an electrophotographic photoconductor. We studied in combination.

 Regarding the electrophotographic apparatus using the electrophotographic photosensitive member of the present invention, the contact charging method using a magnetic brush charger is a voltage control method, so that the width of the surface potential of the electrophotographic photosensitive member is reduced. It became possible, and it was found that the potential unevenness became inconspicuous. Therefore, it has been found that the combination with the electrophotographic photosensitive member according to the present invention can achieve both high level of suppression of potential unevenness and high durability without peeling of the layer. .

Hereinafter, the present invention will be described in detail with reference to the drawings as necessary. << a-Si photoconductor according to the present invention >>

 Fig. 4 shows an example of a negatively charged electrophotographic photosensitive member according to the present invention. Fig. 9 shows the content distribution of Group 13 elements (boron atoms) in the periodic table of the negatively charged electrophotographic photosensitive member of the present invention. FIG. 10 is a schematic diagram showing a change in the composition ratio of carbon to silicon constituting the upper blocking layer of the present invention.

 The electrophotographic photosensitive member of the present invention is, for example, a base (401) made of a conductive material such as A'l, stainless steel, etc., connected to the exhaust means as a first step, and can be vacuum-tight equipped with a raw material gas supply means. Installing in a film-forming furnace, decomposing the source gas with high-frequency power, and depositing a photoconductive layer (405) made of at least a non-single crystal material on the substrate as a first layer (402); As a second step, a step of taking out the substrate on which the first layer (402) is laminated and from a film forming furnace, and as a third step, the first layer laminated in the first step is used. A step of removing at least the top of the protrusion (411) on the surface of the layer (402) and, as a fourth step, a vacuum-tight film forming furnace equipped with an exhaust means and a source gas supply means. The base after finishing the third step is installed at least one type. A step of plasma-treating the surface of the first layer (402) with a gas containing a Group 13 element of the periodic table and a dilute gas selected from hydrogen, argon and helium, and a fifth step. As described above, at least the source gas is decomposed by high-frequency power, and a layer made of a non-single-crystal material is stacked on the first layer as the second layer (403).

By forming the film in this manner, the surface of the protrusion (411) generated from the first layer (402) and removed from the top of the head is modified by the plasma treatment on the order of several atoms, and the charged charge is reduced. Therefore, even if the protrusion (41 1) is present, the image does not appear and it is possible to maintain a good image quality. In the present invention, the first layer (402) includes a photoconductive layer (405), and a-Si is used as the material of the photoconductive layer (405). Further, it is desirable to further provide a lower blocking layer (404) and an upper blocking layer (406) on the first layer (402) in order to improve the electrical characteristics.

 In general, it is desirable that the upper blocking layer (406) has a rectifying property by selectively containing a group 13 element from the viewpoint of improving electrical characteristics.

 In addition, a protective layer (407) made of at least a non-single crystal material can be laminated on the first layer (402), whereby the top of the protrusion (41 1) performed in the third step. When performing the process of removing the head, the process of removing the top of the head can be performed without damaging the surface of the photoreceptor.

 Note that the second layer (403) is a surface protective layer made of at least a non-single crystal material, and is a silicon carbide layer containing at least carbon atoms or silicon atoms, or a non-carbon material containing carbon atoms as a base material. Single crystal material, for example, a-C (H). This surface protective layer can improve the abrasion resistance and scratch resistance of the electrophotographic photosensitive member. .

Further, in the photoconductor according to the present invention, as shown in FIG. 4, the abnormally grown portion in the first layer does not reach the second layer, and as shown in FIG. The composition ratio of carbon to silicon constituting the layer (406) increases toward the surface side, and as shown in FIG. 9, in the interface region (413) between the first layer and the second layer. The content distribution of group 13 elements of the periodic table has a peak. In addition, the peak is preferably 5.0 × 10 ¹⁷ pieces / cm ³ or more and 1.0 × 10 ²¹ pieces / cm ³ or less from the viewpoint of image defect reduction and electrical characteristics. This value can be obtained by using a composition analyzer such as SIMS (secondary ion mass spectrometry). Here, since it is the peak value of the interface region, it is not as a percentage of other constituent elements. The absolute value is displayed.

<< Shape and Material of Substrate According to the Present Invention >> The shape of the substrate (401) shown in FIG. 4 may be as desired according to the driving method of the electrophotographic photosensitive member.

 For example, it may be a smooth or uneven surface cylindrical or plate-like, endless belt-like, and its thickness is appropriately determined so that a desired electrophotographic photosensitive member can be formed. When flexibility as a photoconductor is required, it can be made as thin as possible within a range where the function as a substrate can be sufficiently exhibited. However, the substrate is usually 0.5 mm or more for the cylindrical shape and ΙΟ μ-m or more for the plate shape and endless belt shape in terms of mechanical strength in terms of manufacturing and handling.

 As the base material, conductive materials such as A1 and stainless steel are generally used. However, for example, various plastics, glass, ceramics, etc., especially those that do not have conductivity, at least the following conductive materials are photoconductive. A material imparted with conductivity by vapor deposition on the surface on which the layer is formed can also be used.

 In addition to the above, examples of the conductive material include metals such as Cr, Mo, Au, In, Nb, Te, V, Ti, PPd, and Fe, and alloys thereof. Examples of the plastic include films or sheets of polyester, polyethylene, polycarbonate, cellulose acetate, polypropylene, polychlorinated butyl, polystyrene, and polyamide.

 << First layer according to the present invention >>

 As for the first layer (402) shown in FIG. 4, in the present invention, a non-single crystal material (“a-Si (H, X)”) containing silicon atoms as a base and further containing hydrogen atoms and / or halogen atoms is used. (Abbreviated).

The photoconductive layer (405) can be formed by plasma CVD, sputtering, ion plating, etc. The film thus prepared is particularly preferable because a high-quality film can be obtained. In this method, Si H ₄ , Si ₂ H ₆ , Si ₃ H ₈ , Si ₄ H ₁₀ or the like, or silicon hydride (silanes) that can be gasified is used as a source gas. It can be used by decomposing these gases with high frequency power. Further, Si H 4 and S i ₂ H ₆ are preferable from the viewpoint of easy handling at the time of layer preparation and good Si supply efficiency.

 At this time, the temperature of the substrate is preferably maintained at a temperature of about 200 ° (up to 450 ° C., more preferably about 250 ° C. to 350 ° C. This promotes surface reflection on the surface of the substrate. This is to sufficiently relax the structure.

Similarly, the optimum range of the pressure in the reaction vessel is appropriately selected according to the layer design.In normal cases, 1 Χ1 (Γ ² -1 X10 ³ Pa, preferably 5 Χ1 (Γ ² -5 X10 ² Pa, more preferably 1 X10 - and ^{1 ~ 1 X 1Ό 2 P a} .

In order to improve the characteristics, it is preferable to form a layer by mixing a desired amount of a gas containing H ₂ or a halogen atom with these gases. Halogen raw materials Effective materials for supply include fluorine gas (F ₂ ) and intermetallic compounds such as B r F, C 1 F, C 1 F ₃ , B r F ₃ , B r F ₅ , IF ₅ , IF ₇ etc. Silicon compounds containing halogen atoms, as a what is called silane derivatives substituted with halogen atoms include, for example, be ani gel as preferred _{S i F 4, S i 2} F 6 silicon fluorides force such as ^s it can.

Further, these raw material gases for supplying silicon may be diluted with a gas such as H ₂ , He, Ar, or Ne if necessary.

 The layer thickness of the photoconductive layer (405) is not particularly limited, but about 15 to 50 μm is appropriate considering the manufacturing cost.

Similar to the photoconductive layer (405), the upper blocking layer (406) can be formed by a plasma CVD method, a sputtering method, an 'ion plating method, or the like. Films made using the force S and plasma CVD methods are particularly preferred because high quality films can be obtained. Use Si gas source such as Si H ₄ , Si ₂ H ₆ , Si ₃ H ₈ , Si ₄ H ₁₀ , or silicon hydride (silanes) that can be gasified. However, SiH ₄ and Si ₂ H ₆ are preferable from the viewpoints of easy handling during layer preparation and good Si supply efficiency. Further, the upper blocking layer may be a layer made of a non-single crystal material based on silicon atoms, but a silicon carbide layer is preferable in consideration of electrical characteristics. As a carbon source for producing the silicon carbide layer, CH ₄ , C ₂ H ₂ , C ' ₂ Η 4, C ₂ Η ₆ , C ₃ Η ₈ , C ₄ Η ₁₀ , etc. can be used. CH ₄ , C ₂ H ₂ , and C ₂ H 6 are preferable from the standpoint of C supply efficiency. '

The upper blocking layer (406) blocks the intrusion of charges from the surface side to the first layer (402) side when the electrophotographic photosensitive member is subjected to a charging process with a constant polarity on its free surface. It has a function that does not exhibit such a function when it is charged with the opposite polarity. In order to provide such a function, the upper blocking layer (406) needs to appropriately contain impurity atoms for controlling conductivity. As an impurity atom used for such a purpose, a Group 13 atom can be used in the present invention. Specific examples of such group 13 atoms include boron (B), aluminum (A 1), gallium (Ga), indium (In;), and tarium (T 1). · Boron (B) is particularly suitable. Examples of the boron supply source include BC 1 ₃ , BF ₃ , BB r ₃ , B ₂ H _6, etc., but B ₂ H, ₆ is preferable from the viewpoint of ease of handling.

The necessary content of impurity atoms controlling the conductivity inherent in the upper blocking layer (406) is not generally determined by the composition and manufacturing method of the upper blocking layer (406). Contains 100 atomic ppm or more of the total number of constituent elements, It is preferable to be 30000 atoms ppm or less.

 The atoms controlling the conductivity contained in the upper blocking layer (406) may be uniformly distributed in the upper blocking layer (406), or nonuniformly in the layer thickness direction. It may be contained in a distributed state. However, in any case, in the in-plane direction parallel to the surface of the substrate, it is necessary to contain evenly in a uniform distribution from the point of achieving uniform characteristics in the in-plane direction. .

 The upper blocking layer (406) has a carbon composition ratio with respect to silicon constituting the upper blocking layer (406) from the photoconductive layer (405) side toward the protective layer (407). Thus, increasing from the surface side is more preferable from the viewpoint of suppressing potential unevenness.

In order to further improve the characteristics, the first layer (402) may have a plurality of layers. For example, the lower blocking layer (t04) is generally based on a-Si (H, X) and is conductive by containing a Group 15 element in the periodic table (hereinafter also referred to as Group 15 element). It is possible to control the mold and to have a blocking ability against the carrier from the substrate side. In this case, if necessary, the stress is adjusted by containing at least one element selected from C, N, and O, and the function of improving the adhesion of the photoconductive layer (405) is provided. You can also. Examples of the element used as a dopant for the lower blocking layer (404) in the present invention include a Group 15 element, and the effective use as a raw material for introducing the Group 15 atom is the introduction of a phosphorus atom. as use, PH _3, P ₂ H 4 hydrogenation such as _{phosphorus, PF 3, PF 5, PC} 1 3, PC 1 5, PB r 3, P 1 3 halogens, such as phosphorus, include further PH ₄ 1, etc. It is done. In addition, NO, NO ₂ , N ₂ , NH 3 and the like are effective as starting materials for introducing Group 15 atoms for introducing nitrogen atoms.

The content of the dopant atoms is preferably 1 1 (Γ ² to 1 X 10 ⁴ Child pp m, more preferably 5 Χ 1 (Γ ² to 5 X 10 ³ atoms pp m, optimally IX 10 ^-1 to 1 X 10 ³ atoms pp m.

 Further, a protective layer (407) made of at least a non-single crystal material may be provided on the outermost surface of the first layer (402) of the present invention. The protective layer (407) may be a non-single crystal material based on silicon atoms, but a silicon carbide layer is preferred in view of electrical characteristics. With this protective layer (407), the abrasion resistance and scratch resistance of the electrophotographic photosensitive member can be improved.

 Further, any frequency can be used as the discharge frequency used in the plasma CVD method when the first layer (402) is laminated, and it is industrially referred to as an RF frequency band of 1 MHz or more, 50 Even a high frequency lower than MHz can be suitably used even at a frequency higher than 50 MHz and lower than 450 MHz called the VHF band.

 In addition, it is indispensable to remove the top of the protrusion (411) existing on the surface of the first layer (402) and make it flat to reduce image defects. Figure 2 shows an example of the protrusion after removing the crown. Removal of the top of the head is preferably performed up to the level line (220) from the viewpoint of reducing image defects and improving adhesion. Further, the protrusion (211) after the removal of the top of the head is in a state where the photoconductive layer is exposed due to the relationship between the height of the protrusion (211) and the film thickness of the first layer.

 In addition, the processing for removing the top of the head includes means for removing the head by melting the head, such as alkali etching, but polishing is preferred from the viewpoint of workability and uniformity. Such a polishing process can be performed by a surface polishing apparatus described later.

In addition, the treatment of bringing the electrophotographic photosensitive member into contact with water before installing it again in the film forming furnace is for the purpose of improving the adhesion of the second layer (403), which will be described later, and reducing dust adhesion. It ’s good. Specific treatment methods include clean cloth and paper It is better to clean the surface with a method of cleaning with an organic solvent or water. In particular, in view of environmental considerations in recent years, water washing with a water washing apparatus described later is more preferable.

 << Plasma treatment according to the present invention >>

 In the plasma treatment according to the present invention, after the first layer is formed, the discharge is temporarily stopped, the substrate is taken out of the film formation furnace, and the protrusion on the surface of the first layer is at least at the top of the top. After removal, it is placed in a vacuum-tight film-forming furnace.

 Specifically, plasma is generated in a dilute gas atmosphere consisting of at least one gas selected from Group 13 elements of the periodic table and hydrogen, argon, and helium.

 The protrusion surface from which the top of the head has been removed and the photoconductive layer has been exposed is modified to the order of several atoms by this plasma treatment, and becomes an interface having a blocking ability against charged charges. Since this interface can be formed between the first layer and the second layer, it is possible to maintain the effect of reducing image defects even if the upper blocking layer is not laminated as the second layer. It will be possible ... In addition, since it is not necessary to stack the upper barrier layer as the second layer, a layer having a low carbon content is stacked after a layer having a high carbon content, thereby reducing the adhesion. Can be prevented.

 The reason why the effect of reducing image defects is maintained by this plasma treatment is that the surface of the protrusion is modified by the plasma treatment to the order of several atoms, and the interface has a blocking ability against the charged charge. This is thought to be due to the fact that it was able to prevent intrusion.

In this plasma treatment, the first layer is stacked in a vacuum-tight film-forming furnace, and the base from which the top of the protrusion is removed is placed. At least one group ₁₃ element in the periodic table is added. Choose from gas, hydrogen, argon, helium This is done by generating plasma in a dilute gas atmosphere consisting of at least one. Any frequency can be used as the discharge frequency when generating the plasma. Industrially, even a high frequency of 1 MHz or more and less than 50 MHz called the RF frequency band is called the VHF band. It can be suitably used even at a high frequency of 50 MHz or more and 450 MHz or less. Examples of the gas containing Group 13 element of the periodic table include BC 1 ₃ , BF ₃ , BB r ₃ , B ₂ H 6, etc., but B ₂ H ₆ gas is preferable from the viewpoint of easy handling. The content of boron atoms in the total gas flow rate is preferably 2.0 × l (T ⁴ mol% or more and 2.0 × 10 — ² mol% or less in view of image defect reduction effect and electrical characteristics.

 '《Second layer according to the present invention》

 In the second layer (403) according to the present invention shown in FIG. 4, after the first layer (402) is formed, the discharge is temporarily stopped, the substrate is taken out of the film formation furnace, and the first layer surface The top of the protrusion is removed from the protrusion, and after the plasma treatment, the layers are stacked.

 The second layer (403) of the present invention is a surface protective layer (408) made of at least a non-single crystal material. The surface protective layer (408) can improve the abrasion resistance and scratch resistance of the electrophotographic photosensitive member.

The surface protective layer (408) can be formed by the plasma C VD method, the sputtering method, the ion plating method, etc., like the photoconductive layer (405). This is preferable because a high-quality film can be obtained. Si sources include Si H ₄ , Si ₂ H ₆ , Si ₃ H ₈ , Si ₄ H io and other gaseous silicon hydrides (silanes), or gasifiable silicon hydride ( Silanes) can be used, but Si H 4 and Si ₂ H ₆ are preferred because they are easy to handle at the time of layer preparation and have good Si supply efficiency. In addition, the surface protective layer is based on silicon atoms. Of these, a silicon carbide layer containing carbon atoms and silicon atoms, and a non-single crystal material based on carbon atoms, such as aC (H), are preferred. The carbon source used here is tl 4, ^ 2 H 2 C Η 4 2 Η 6> and 3 ng, 4 χ χο, etc., and CH 4 and C _{2 in} terms of the C supply efficiency. Η 2, C ₂ H ₆ is preferred.

 Any frequency can be used as the discharge frequency used in the plasma CVD method when laminating the second layer (403), and it is industrially referred to as an RF frequency band of 1 MHz or more and less than 50 MHz. However, it can be suitably used even at a high frequency of 50 MHz or more and 450 MHz or less, called the VHF band.

Similarly, the optimum range of the pressure in the reaction vessel is also appropriately selected according to the layer design.In normal cases, 1 Χ1 (Γ ² -1 X10 ³ Pa, preferably 5 Χ1 (Γ ² -5 X10 ² Pa, Optimally, it is preferably 1 X10 ^-1 to 1 X10 ² Pa.

 Further, the optimum range of the temperature of the substrate is appropriately selected according to the layer design. In general, it is more preferable to set the temperature lower than the substrate temperature at the time of forming the first layer from the viewpoint of improving adhesion. Specifically, in the case of forming a silicon carbide layer, it is desirable to set the temperature to 100 ° C. to 330 ° C., more preferably 150 ° (: to 270 ° C. Non-single crystal material based on carbon atoms, for example, In the case of aC (H), it is preferable to select 20 ° C. or more and 50 ° C., preferably about room temperature, for example, 25 ° C.

 << a-Si photoconductor film forming apparatus according to the present invention >>

 FIG. 5 is a diagram schematically showing an example of a film forming apparatus for an electrophotographic photosensitive member by an RF plasma CVD method using a high-frequency power source. +

This apparatus is roughly composed of a film forming apparatus (5100), a source gas supply apparatus (5200), and an exhaust apparatus (not shown) for depressurizing the inside of the film forming furnace (5110). The substrate connected to the ground in the deposition furnace (5110) in the deposition apparatus (5100) (5112), a substrate heating heater (5113) and a source gas introduction pipe (5114) are installed, and a high frequency power source (5120) is connected via a high frequency matching box (5115). ,

The raw material gas supply device (5200) includes Si H ₄ , H ₂ , CH ₄ , NO, B ₂ H ₆ , CF 4 and other raw material gas cylinders (5221 to 5226) and valves (5231 to 5236), (5241 to 5246 ), (5251-5256) and mass flow controller (5211-5216), each gas cylinder is connected to the gas inlet pipe (5114) in the film-forming furnace (5110) via pulp (5260) Has been.

 The substrate (5112) is connected to the ground by being placed on the conductive cradle (5123).

 Hereinafter, an example of a procedure for forming an electrophotographic photosensitive member using the apparatus of FIG. 5 will be described.

 The substrate (5112) is set in the film forming furnace (5110), and the film forming furnace (5110) is evacuated by an unillustrated exhaust device (for example, a vacuum pump). Subsequently, the temperature of the substrate (5112) is set to 200 ° C. to 450 ° C., more preferably by the heater for heating the substrate (5113).

Control to the desired temperature between 250 ° C and 350 ° C. Next, make sure that the gas cylinder pulp (5231 to 5236) and the leak pulp (5117) of the film forming furnace are closed in order to flow the raw material gas for forming the photoconductor into the film forming furnace (5110). Check that the inflow valve (5241 to 5246), outflow valve (5251 to 5256), and trap valve (5260) are open, then open the main valve (5118) and the T deposition furnace (5110) and Exhaust the gas supply pipe (5116).

 Then, close the auxiliary valve (5260) and the spilled pulp (5251-5256) when the reading of the vacuum gauge (5119) becomes about 0.1 Pa or less. Then, each gas is introduced from the gas cylinder (5221 to 5226) by opening the valve (5231 to 5236), and each gas pressure is adjusted to 0.2 MPa by the pressure regulator (5261 to 5266). .

Next, the inflow pulp (5241 to 5246) is gradually opened and each gas is mass flow controlled. It is introduced into the controller (5211 to 5216).

 After completing the preparation for film formation by the above procedure, first, for example, a photoconductive layer is laminated as a first layer on the substrate (5112).

 That is, when the substrate (5112) reaches a desired temperature, necessary ones of the outflow valves (5251 to 5256) and the auxiliary pulp (5260) are gradually opened, and each gas cylinder (5221 to 5226) is opened. Then, a desired source gas is introduced into the film forming furnace (5110) through the gas introduction pipe (5114). Next, each mass flow controller (521 1 to 5216) is adjusted so that each source gas has a desired flow rate. At that time, adjust the opening of the main pulp (51 18) while looking at the vacuum gauge (51 19) so that the inside of the film forming furnace (51 10) is at a desired pressure of 13.3 Pa to 1330 Pa. . When the internal pressure is stable, set the high-frequency power supply (5120) to the desired power and, for example, apply high-frequency power with a frequency of 1 Μ ζ ζ to 50 ζ ζ, for example 13.56 ζ Μ ζ, through the high-frequency matching box (51 15). A high frequency glow discharge is generated by supplying the sword electrode (511 1). With this discharge energy, each source gas introduced into the film forming furnace (5110) is decomposed, and a photoconductive layer mainly composed of desired silicon atoms is laminated on the substrate (5112).

 After the formation of the desired film thickness, the supply of high-frequency power is stopped, the outflow valves (5251 to 5256) are closed to stop the flow of each source gas into the film formation furnace (51 10), and the photoconductive layer Finish the lamination.

 Known and known compositions and film thicknesses of the photoconductive layer can be used. Subsequently, when the upper blocking layer is laminated, or when the lower blocking layer is laminated between the photoconductive layer and the substrate (5112), the above operation may be basically performed in advance. The point is to remove the top of the protrusions on the substrate laminated up to the first layer by the procedure described above.

It is preferable to perform treatment with water before laminating the second layer, and specific treatment methods include water washing and organic solvent washing. However, water washing is more preferable in view of environmental considerations in recent years. The method of washing with water will be described later. In this way, washing with water before the second layer is laminated is effective in improving adhesion and reducing dust adhesion. .

 Next, the substrate which has been subjected to the treatment of removing the top of the protrusion and bringing it into contact with water is again returned to the film forming furnace, and plasma treatment and lamination of the second layer are performed.

 << Surface polishing apparatus according to the present invention >>

 FIG. 6 shows an example of a surface polishing apparatus used when removing the top of the protrusion in the manufacturing process of the negatively charged electrophotographic photoreceptor of the present invention. In the configuration example of the surface polishing apparatus shown in Fig. 6, the object to be processed "deposited film surface on cylindrical substrate" (600) has a first layer of a-Si deposited on its surface. Cylindrical substrate, attached to the elastic support mechanism (620).

In the apparatus shown in FIG. 6, for example, a pneumatic holder is used as the elastic support mechanism (620). Specifically, a pneumatic holder manufactured by Pridestone (trade name: air picker, model number: P 045 TCAX 820) Is used. The pressure inertia roller (630) winds the polishing tape (631) and presses it against the surface of the workpiece (600). · The polishing tape (631) is supplied from the feed roll (632) and collected by the scraping roll (633). The feed speed is adjusted by a constant feed roll (634) and a capstan roller (635), and the tension is also adjusted. As the polishing tape (631), what is usually called a rubbing tape is preferably used. When processing the surface of a-Si photoconductive layer or upper blocking layer or protective layer, the rubbing tape contains Si C, A 1 ₂ O ₃ , Fe ₂ O ₃ etc. as abrasive grains Used. Specifically, Fuji Film's rubbing tape LT-C 2000 was used. The pressure elastic roller (630) is made of materials such as neoprene rubber and silicone rubber, and conforms to JIS standards (JIS K 6253 N method). The rubber hardness is in the range of 20-80, more preferably in the range of rubber hardness 30-40. Further, the shape of the roller part is preferably such that the diameter of the central part is slightly larger than the diameter of both end parts in the longitudinal direction, for example, the difference in diameter between the two is 0.0 to 0.6 mm, more preferably 0.2 to 0.4 mm. A shape that falls within this range is preferred. The pressure elastic roller (630) is a polishing tape that is pressed against a rotating workpiece “deposition film surface on a cylindrical substrate” (600) in a pressure range of 0.05 MPa to 0.2 MPa. (, 631) For example, the above-mentioned rubbing tape is fed to polish the surface of the deposited film.

 For surface polishing performed in the atmosphere, it is also possible to use wet polishing means such as puff polishing in addition to the means using the polishing tape. In addition, when using wet polishing means, there is a process for cleaning and removing the liquid used for polishing after polishing, and at that time, the surface is brought into contact with water and cleaned. can do.

 << Water cleaning apparatus according to the present invention >>

 An example of the water cleaning apparatus used in the present invention is shown in FIG.

The processing apparatus shown in FIG. 7 includes a processing unit (702) and a member-to-be-processed transport mechanism (703). The processing section (702) is composed of a processing member input stand (71 1), a processing member cleaning tank (721), a pure water contact tank (731), a drying tank (741), and a processing member unloading base (751). ing. Both the washing tank (721) and the pure water contact tank (731) are provided with a temperature control device (not shown) for keeping the temperature of the liquid constant. The transfer mechanism (703) includes a transfer rail (765) and a transfer arm (761). The transfer arm (761) is a moving mechanism (762) that moves on the rail (765) and a chucking that holds the base body (701). It consists of an air cylinder (764) for moving the mechanism (763) and the chucking mechanism (763) up and down. The substrate (701) placed on the input table (711) is transferred to the cleaning tank (721) by the transfer mechanism (703). Surfactant in the cleaning tank (721) The adhering oil and powder are cleaned. Next, the substrate (701) is transported to the pure water contact tank (731) by the transport mechanism (703), and pure water with a resistivity of 175 kQm (17.5 MQcm) maintained at a temperature of 25 ° C is supplied. Sprayed from nozzle (732) with a pressure of 4.9 MPa. The substrate (701) after the pure water contact step is moved to the drying tank (741) by the transport mechanism (703), and is dried by blowing high-temperature high-pressure air from the nozzle (742). The substrate (701) after the drying process is carried to the unloading base (751) by the transport mechanism (703).

 << Electrophotographic apparatus according to the present invention >>

 An example of an electrophotographic apparatus using the negatively charged electrophotographic photosensitive member of the present invention is shown in FIG.

 FIG. 8 is a schematic view showing an example of an image forming process of the electrophotographic apparatus, and the photoconductor (801) rotates to perform a copying operation. Around the photoreceptor (801) are a magnetic brush injection charger (803), a developer (804), a transfer paper supply system (805), a transfer charger (806 (a)), a separation charger (806 (b) )), A cleaning unit (807), a transport system (808), a static elimination light source (809), and the like.

 Hereinafter, the image forming process will be described more specifically. The photoconductor (801) is uniformly charged by the magnetic brush electrode (803). Next, a static latent image is formed by light emitted from the laser unit (818) and passing through the mirror (819), and a negative polarity toner is supplied from the developing unit (804) to the latent image to form a toner image. Is done. The signal from the C C D unit (817) is used to control the laser unit (818). That is, the light emitted from the lamp (810) is reflected by the document (812) placed on the platen glass (81 1), passes through the mirrors (813), (814), and (815), and passes through the lens unit. The image is formed by the (816) lens and converted to an electrical signal by the CCD unit (817).

On the other hand, through the transfer paper supply system (805), by the registration roller (822) The transfer material P, adjusted in timing and supplied in the direction of the photoconductor (801), is separated from the toner in the gap between the transfer charger (806 (a)) and the photoconductor (801) to which high voltage is applied. A positive electric field having a reverse polarity is applied, whereby a negative polarity toner image on the surface of the photoreceptor is transferred to the transfer material P. Next, the transfer material P passes through the transfer conveyance system (808) to the fixing device (824) by the separation charger (806 (b)) to which the high-voltage AC power is applied, and the toner image is fixed and carried out of the device. It is done. '

Example

 Hereinafter, the present invention will be described in detail with reference to Examples and Comparative Examples. The present description is not limited to these examples.

 (Example 1)

Using the RF plasma CVD a-Si photoconductor deposition system shown in Fig. 5, at least a non-single crystal as the first layer on an A 1 substrate with an outer diameter of 80 mm under the conditions shown in Table 1 A lower blocking layer made of a material and a photoconductive layer made of at least a non-single crystal material were laminated. Thereafter, the substrate on which the first layer is laminated is once taken out from the film forming furnace and exposed to the atmosphere, and then the protrusion on the surface of the first layer is subjected to a polishing process to remove at least the top of the head, A treatment for bringing the surface of the first layer into contact with water is performed, and then a substrate on which the first layer is laminated is placed in a film forming furnace, and the results shown in Table 2 before the second layer is laminated Plasma treatment was performed by changing the flow rate of B ₂ H ₆ gas (2850 ppm / H ₂ ) as shown in Table 3 to the amount of B (content of boron atoms in the total gas flow rate introduced), A negatively charged electrophotographic photosensitive member was produced by laminating the second layer under the conditions shown in Table 1. The charging ability of the negatively charged electrophotographic photoreceptor thus prepared was evaluated by the following method. The results are shown in Table 3. As shown in the table, Examples 1-1 to 1-8 were performed with respect to the B content of 1.0 Χ 1 (Γ ^{4 to} 3.0 Χ 1 (Γ ² [πι ol%]). In addition, the peak value of the boron content distribution in the interface region between the first layer and the second layer of the produced photoreceptor was analyzed using SIMS (secondary ion mass spectrometry). Since the peak value obtained here is the peak value in the interface region, the absolute value is displayed instead of the ratio between boron and other constituent elements. The results are also shown in Table 3.

 《Chargeability》

 The produced electrophotographic photosensitive member was charged in an electrophotographic apparatus and charged, and the surface potential meter of the electrophotographic photosensitive member was measured with a surface potential meter installed at the position of the imager to obtain a charging ability. At this time, the charging conditions (DC applied voltage to the charger, superimposed AC amplitude, frequency, etc.) were constant for comparison. The obtained results were ranked by relative evaluation using the value in Example 1-11 as the standard (100%).

 A… 105% or more

B… Less than 105%

table 1

Gas type and flow rate 1st layer 2nd layer Lower block

 Photoconductive layer

SiH ₄ [ml / min (normal)] 100 100 10

H ₂ [ml / min (normal)] 600 800

 NO [ml / min (normal)] 8

CH ₄ [ml / min (normal)] 600 Substrate temperature [° C] 260 260 180 Internal pressure in reaction vessel [Pa] 64 79 60 High frequency power [W] 100 400 180 Film thickness [μπι;] 3 20 0.8 Table, Type and flow rate Plasma treatment

H ₂ [ml / min (normal)] 796

 B [m ol%]

 Change

[Β ₂ Η ₆ [ρρώ] (vs. H ₂ )]

Substrate temperature [° C] 180

Reaction vessel internal pressure [Pa] 87

High frequency power [W] 400 Table 3

From the results in Table 3, the amount of B (content of boron atoms in the total gas flow rate introduced) at the time of the plasma treatment performed before laminating the second layer is shown in Example 1 1 2 to Example 1 1 7 2.0 X l (T ⁴ mol% or more and 2.0 X l (T ² mol% or less) was found to be the optimum range. Also, boron content in the interface region between the first layer and the second layer The optimum range of the peak value of the quantity distribution should be 5.0 x 10 ¹⁷ pieces / cm ³ or more and 1.0 x 10 ²¹ pieces / cm ³ or less in Examples 1 to 2 to Examples 1 to 7. found.

 (Example 2)

 In the procedure of Example 1, a negatively charged electrophotographic photosensitive member was produced under the conditions shown in Table 5 except that the treatment for bringing the surface of the first layer into contact with water was not performed, and the cost, adhesion, The following methods were used to evaluate polishing scratches, charging ability, image defects, and potential unevenness. The results are shown in Table 18.

 (Example 3)

In the procedure of Example 1, a negatively charged electrophotographic photosensitive member was manufactured under the conditions shown in Table 6 except that the first layer was changed by adding an upper blocking layer made of at least a non-single crystal material as a first layer. The following methods were used to evaluate the cost, adhesion, polishing scratches, charging power, image defects, and potential unevenness. The results are shown in Table 18. (Example 4)

 In the procedure of Example 3, a negatively charged electrophotographic photosensitive member was produced under the conditions shown in Table 7 except that a protective layer made of at least a non-single crystal material was added as the first layer and the layer was laminated. The following methods were used to evaluate the following characteristics: adhesiveness, adhesion, polishing scratches, charging ability, image defects', and potential unevenness. The results are shown in Table 18.

 (Example 5)

In the procedure of Example 4, by changing the B ₂ H ₆ flow rate of the upper blocking layer laminated as the first layer as shown in Table 4, the period with respect to the total number of constituent elements contained in the upper blocking layer Photoreceptors 5- :! to 5-6 with varying Group 13 element (boron) content are produced under the conditions shown in Table 8. Cost, adhesion, polishing scratches, charging ability, image Defects and potential unevenness were evaluated by the following methods. The results are shown in Table 18.

 The content of the group 13 element (boron) in the periodic table with respect to the total number of constituent elements of the photoreceptors 5-1 to 5-6 was measured using SIMS (secondary ion mass spectrometry). The results are shown in Table 4.

 Table 4

(Example 6)

In the procedure of Example 4, the second layer is a non-carbon material. A negatively charged electrophotographic photosensitive member was manufactured under the conditions shown in Table 9 with only the point of laminating the single crystal material (a-C (H)), and cost, adhesion, polishing scratches, charging ability, image defects The potential unevenness was evaluated by the following method. The results are shown in Table 18. ■

 (Examples 7 to 1 1)

 In the procedure of Example 4, the upper blocking layer to be laminated as the first layer was changed only in that the composition ratio with respect to the constituent silicon was laminated by changing as shown in FIG. 10 in the layer thickness direction. Under the conditions shown in Table 10 to Table 14, the negatively charged electrophotographic photoconductors of Examples 7 to 11 were prepared, and the cost, adhesion, polishing scratches, charging ability, image defects, and unevenness in the position of the surface were measured. The following method was used for evaluation. The results are shown in Table 18.

 (Comparative Example 1) '

 In the procedure of Example 1, a negatively charged electrophotographic photosensitive member was produced by changing only the point that the plasma processing performed before laminating the second layer was performed under the conditions shown in Table 15. The following methods were used to evaluate adhesion, polishing scratches, charging ability, image defects, and potential unevenness. The results are shown in Table 18.

 (Comparative Example 2)--'In the procedure of Example 4, the upper surface blocking layer made of a non-single-crystal material and the surface protective layer were used as the second layer without performing the plasma treatment of the substrate surface on which the first layer was laminated. A negatively charged electrophotographic photosensitive member was manufactured under the conditions shown in Table 16 with the point where the layers were laminated, and the cost, adhesion, polishing scratches, charging ability, image defects, and potential unevenness were evaluated using the following methods. Went. The results are shown in Table 18.

 '(Comparative Example 3)

The conditions shown in Table 17 were changed in the procedure of Comparative Example 2 except that the second layer was added with an intermediate layer made of at least a non-single crystal material. A negatively charged electrophotographic photosensitive member was prepared and evaluated for cost, adhesiveness, polishing scratches, charging performance, image defects, and potential unevenness by the following methods. The results are shown in Table 18.

 The negatively charged electrophotographic photosensitive member produced in Example 1 was also evaluated for the cost, adhesion, polishing scratches, charging ability, image defects, and potential unevenness by the following methods. The results are also shown in Table 18.

 《Cost》

 Comparative Example 3 was used as a reference for relative evaluation. A decreased by 15% or more compared to Comparative Example 3, B decreased by 10% or more and less than 15% compared with Comparative Example 3, C represents 5% or more compared with Comparative Example 3 A decrease of less than 10%, D indicates a decrease of 1% or more and less than 5% compared to Comparative Example 3, and E indicates that it is equivalent to Comparative Example 3.

 《Adhesion》

 Adhesion between the first and second layers

Measurement was performed using HEIDON (Type: 14 S). Using this device, the surface of the photoconductor on which each layer is laminated is pulled with a diamond needle, and the layer and the layer adhere to each other with the magnitude of the load applied to the diamond needle when peeling occurs on the photoconductor surface. The power was evaluated. The obtained results were ranked by relative evaluation when the value in Comparative Example 3 was 100%.

 A… 105% or more

 B… 95% or more, less than 105%

 C · Less than 95%

 《Polishing wound》

The surface of the electrophotographic photoreceptor after polishing was observed using an optical microscope. Then, a protrusion with a diameter of about 30 μm is polished to the level line, and scratches caused by polishing extending from the protrusion to the normal part are defined as polishing scratches. The presence or absence was confirmed.

 .. In addition, as a judgment symbol in the table, A is that there are no polishing scratches in the normal part, B is that there are 5 or less minor scratches on the entire surface of the photoconductor, and C is that there are minor scratches on the entire surface of the photoconductor. It shows that 5 or more occurred. · 《Chargeability》

 The prepared electrophotographic photosensitive member was placed in an electrophotographic apparatus for charging, and the surface potential meter installed at the current imager position was used to measure the surface potential of the dark part of the electrophotographic photosensitive member to determine the charging ability. At this time, the charging conditions (DC applied voltage to the charger, superimposed AC amplitude, frequency, etc.) were constant for comparison. For the results, the value in Comparative Example 3 was used as the standard (100%): ranking was performed based on the relative evaluation.

 A… 95% or more

 B… 85% or more, less than 95%

 C… 75% or more, less than 85%

 D… Less than 75%

 《Image defect》

Image defects were evaluated by the number of black spots with a diameter of 0.1 mm or less in a 0% pixel density image. Black spots with a diameter exceeding 0, lmm are mostly caused by dust attached to the support before the start of film formation of the photoconductor. Such image defects are caused by film formation. It is clear from the results of various studies by the present inventors that the dependence on time conditions is small and it is essential to eliminate image defects by improving processes such as dust reduction. For this reason, the evaluation was conducted by focusing on the number of relatively small image defects with a diameter of 0.1 mm or less, which can be affected by the conditions during film formation, except for the current evaluation. The obtained results were ranked by relative evaluation using the value in Comparative Example 1 as a reference (100%). A: Less than 90%

 B… 90% or more

 《Electric potential unevenness》

 Using a Canon i R.6000 (process speed 265 mm / sec) primary charger modified for magnetic brush charging, adjusting the charger so that the dark potential at the developer position is -450 V, and developing Measure the in-plane distribution of the difference between the dark part potential and the bright part potential with the light intensity of the image exposure light source adjusted so that the bright part potential at the detector position is -100 V. The maximum and minimum values of the difference are measured. The difference was defined as potential unevenness. The obtained results were ranked by relative evaluation using the value in Comparative Example 1 as a reference (100%).

 A: Less than 90%

 B… 90% or more

 "Comprehensive evaluation"

 The results obtained from the evaluation of cost, adhesion, and polishing flaws were summed up as 3 points for A rack, 2 points for B rank, 1 point for C rank, 1 rank for D rank, and 0 rank for E rank. Based on the score, ranking was performed as follows.

 1 6 points or more, 5 or more A ranks, no D or E ranks (Excellent)

 A ~ 1 5 points or more, 4 ranks A, 4 ranks, no D and E ranks (very good)

 B ~ 14, or more, C rank is 1 or less, D, E rank is missing (excellent)

 C ~ 1 2 or more points, 2 or less C ranks, no D or E ranks (good)

D ~ 1 Less than 2 points or one with D or E rank (no problem in practical use) Table 5

Table 7 First layer Plasma treatment Second layer Gas type and flow rate Lower blocking Photoconduction Upper blocking

 Protective layer Surface protective layer

SiH ₄ [ml / min (normal)] 100 100 200 10 10

¾ [ml / min (normal)] 600 800 778

B ₂ [ppm] (vs SiH ₄ ) 900

B [mol%] 1.56 X ² [B ₂ H ₆ [ppm] (vs. H ₂ )] [80]

NO [ml / min (normal)] 8

CH ₄ [ml / min (normal)] 150 600 500 Substrate temperature [° C] 260 260 260 260 180 180 Anti-Jfe inner pressure [Pa]. 64 79 60 60 87 60 High frequency power [W] 100 400 300 180 400 180 Film thickness [μιη] 3 20 0.2 0.5 0.8

Table 8 First layer Plasma treatment Second layer Gas type and flow rate Lower block Photoconductivity Upper block

 Protective layer Table IS protective layer

S iH ₄ [ml / min (normal)] 100 100 90 10 30

H ₂ [ml / min (normal)] 600 800 789

B ₂ H ₆ [ppm] (vs. SiH ₄ ) change

B [m ol%] 7.89 X ³

[B ₂ H ₆ [ppm] (vs. ¾)] [40]

 NO [ml / min (normal)] 8

CH ₄ [ml / min (normal)] 90 600 600 Substrate temperature [° C] 260 260 260 260 180 180 Reaction vessel internal pressure [Pa] 64 79 60 60 87 60 High frequency power [w] 100 400 300 180 400 180 Film thickness [μπι] 3 20 0.2 0.5 0.8

Table 9

Ten

Gas type and flow rate Upper blocking layer

SiH ₄ [ml / min (nornial)] 10 → 10 10 → 10

H ₂ [ml / min (normal)]

B ₂ H ₆ [ppm] (vs. SiH ₄ ) 0 → shelf → 0

B [m ol%]

 o

[B ₂ H ₆ [ppm] (vs. ¾)] o T

 NO [ml / min (normal)] ο

CH ₄ [ml / min (normal)] 0 → 800 800 → 700 700 → 600 Substrate temperature [° C] 260 260 260 Reaction vessel internal pressure [Pa] 60 60 60 High frequency power [w] 300 300 300 Film thickness [μπι] 0.1 0.08 0.1

Gas types and flow rates Upper blocking layer ''

S iH ₄ [ml / min (normal)] 10 → 10 10 → 10

H ₂ [ml / min (normal)]

B ₂ H ₆ [ppm] (vs. SiH ₄ ) 0 → 400 → 0

 B [m ol%]

[B ₂ H ₆ [ppm] (vs. H ₂ )] Ό

 Ο

NO [ml / min (normal)] ο

CH ₄ [ml / min (normal)] '0 → 400 400 → 550 550 → 600 Substrate temperature [° C] 260 260. 260 Pressure inside reaction vessel [Pa] 60 60 60 High frequency power [w] 300 300 300 Film thickness [ μιη] 0.1 0.08 0.1

1 2

Gas type and flow rate Upper blocking layer

S iH ₄ [ml / min (normal)] 100 → 25 25 → 15 15 10

¾ [ml / min (normal)]

B ₂ H ₆ [ppm] (vs. SiH ₄ ) 0 → 400 → 0

 B [m ol%]

[B ₂ H ₆ [ppm] (vs. ¾)]

 NO [ml / min (normal)]

CH ₄ [ml / min (normal)] 0 → Scratch 400 → 500 500 → 600 Substrate temperature [° C] 260 260 260 Reaction vessel internal pressure [Pa] 60 60 60 High frequency power [W] 300 300 300 Film thickness [μιη] 0.1 0.08 0.1

13

7

 44 1 4

Gas type and flow rate Upper blocking layer

SiH ₄ [ml / mm (noraial)] 100 → 30 30 → 60 60 → 10

 ¾ [ml / min (normal)]

B ₂ H m] (vs SiH ₄ ) 0 → 400 → 0

 B [m ol%]

[B ₂ H ₆ [ppm] (vs. ¾)]

 NO [ml / min (normal)]

CH ₄ [ml / min (normal)] 0 → 400 400 → 500 500 → 600

Substrate temperature [° C] 260 260 260

Reaction vessel internal pressure [Pa]-60 60 60

High frequency power [w] 300 300 300

Film thickness [μιη] 0.1 0.08 0.1

Table 1 5 1st layer 2nd layer

 7 Razma

Gas type and flow rate Lower blocking Photoconductive

 Treatment surface

SiH ₄ [ml / min (normal)] 100 100 10 [ml / min (normal)] 600 600 800

B ₂ H ₆ [ppm] (vs. SiH ₄ )

 NO [ml / min (normal)] 8

CH ₄ [ml / min (normal)] 550 Substrate temperature [° C] '260 260 180 180 Reaction vessel internal pressure [Pa] 64 79 87 60 High frequency power [W] 100 350 400 180 Film thickness [μηι] 3 20 0.8

Table 1 6

 1st layer 2nd layer Gas type and flow rate 'Lower blocking Photoconduction Upper blocking

 Protective upper blocking layer

Siri ₄ [ml / min (normal)] 100 100 90 10 90 50

H ₂ rml / mm (normal)] 600 800

B ₂ H ₆ [ppm] (vs. SiH ₄ ) 300 300

 NO [ml / mininormal)] 8

CH4 [ml / mm (normal)] 90 600 90 600 Substrate temperature [° C] 260 260 260 260 180 180 Reaction vessel internal pressure [Pa] 64 79 60 6.0 60 60 High frequency power [W] 100 400 300 180 300 180 Film thickness [μιη] 3 20 0.2 0.5 0.2 0.8

Table 1 7 1st layer 2nd layer

Gas type and flow rate Lower blocking Upper blocking Upper blocking surface protection Summary layer Intermediate layer

S iH ₄ [ml / min (normal)] 100 100 90 10 10 90 10

H ₂ [ml / min (normal)] 600 800

B ₂ H ₆ [ppm] (vs. SiH ₄ ) 300 300

 NO [ml no min normal]] 8

CH ₄ [ml / min (normal)] 90 600 600 90 600 Substrate temperature [° C] 260 260 260 260 180 180 180 Reaction vessel internal pressure [Pa] 64 79 60 60 60 60 60 High frequency power [W] 100 400 300 180 180 300 180 Film thickness [μιη] 3 20 0.2 0.5 0.2 0.2 0.8

Table 1 8

As can be seen from Table 18 in Comparative Examples 2 and 3, the plasma treatment prior to laminating the second layer is not performed, and the upper blocking layer is laminated as the second layer. As a result, the sex decreased. In addition, the upper blocking layer was laminated as the second layer, and the intermediate layer had to be laminated to maintain a certain degree of adhesion, resulting in an increase in the overall cost.

On the other hand, in Examples 1 to 11, the surface of the protrusion subjected to plasma treatment on the surface of the first layer before laminating the second layer to at least remove the top of the head However, it is improved in the order of several atoms by plasma treatment. As a result, the charging charge can be prevented from penetrating into the protrusion, and the image defect can be prevented without laminating the upper blocking layer as the second layer. It was possible to maintain the reduction effect. This eliminates the need to stack the upper blocking layer as the second scrap, thus reducing the overall cost and improving adhesion without reducing the image defect reduction effect compared to the comparative example. We were able to.

 From the results of Example 5, the content of the Group 13 element (boron) in the periodic table with respect to the total number of constituent elements is 100 atoms ppm or more and 30000 atoms ppm or less from the viewpoint of charging ability. It turned out to be preferable. Further, from the results of Examples 7 to 11, it was found that the potential unevenness was improved by making the composition ratio of carbon to silicon constituting the upper blocking layer to increase toward the surface side.

 In addition, from the results of Examples 1 and 2, it was confirmed that the adhesion and charging ability were improved by performing the treatment of bringing the surface of the first layer into contact with water. Next, the negatively charged electrophotographic photosensitive member produced in Example 4, Example 9, and Comparative Example 1 was evaluated only for potential unevenness by the following method. The results are shown in Table 19.

 《Electric potential unevenness》

Using a Canon iR 6000 (process speed 265 mm / sec) with a corona charger as the primary charger, adjusting the charger so that the dark part potential at the developer position is -450 V, and adjusting the brightness at the developer position. In the state where the light intensity of the image exposure light source is adjusted so that the partial potential is -100 V, the in-plane distribution of the difference between the dark portion potential and the bright portion potential is measured, and the difference between the maximum value and the minimum value of the difference is measured as potential unevenness. It was. For the results obtained, the value of Comparative Example 1 when using a Canon i R 6000 (process speed 265 mm / sec) primary charger modified for magnetic brush charging is the standard (100%) And ranked by relative evaluation I did

 A: Less than 90%

 B "-90% or more, less than 110%

 C… 110% or more

 : 1 9 In Example 4 In Example 9 In Comparative Example 1

 Produced photoconductor Produced photoconductor Produced photoconductor Potential unevenness CBC As shown in Tables 18 and 19, it was confirmed that the suppression of potential unevenness was further improved by using a magnetic brush charger. .

 In addition, when argon or helium was used as a dilution gas at the time of the plasma processing performed before the second layer was laminated, the same effect as in the above-described example was obtained. This application was filed on August 5, 2000, Japan patent application number 2 0 0 4— 2 3 9 4 9 0 and August 5, 2000 This claim claims priority from Japanese Patent Application No. 2 0 0 5-2 2 7 7 5 0, the contents of which are incorporated herein by reference.

Claims

The scope of the claims

1. In a method of manufacturing a negatively charged electrophotographic photosensitive member including a layer made of a non-single crystal material,-As a first step, a vacuum-tight film-forming furnace connected to an exhaust means and provided with a source gas supply means A cylindrical substrate having a conductive surface is placed inside, the source gas is decomposed by high-frequency power, and a photoconductivity consisting of at least a non-single crystalline material as the first layer is formed on the substrate. A step of depositing a layer, and a step of removing the substrate on which the first layer is laminated from the film forming furnace as a second step;

 As a third step, a process of removing at least the top of the protrusion on the surface of the first layer laminated in the first step; and

 As the fourth step, the substrate after completion of the third step is placed in a vacuum-tight film-forming furnace equipped with an evacuation means and a source gas supply means, and at least one group 13 of the periodic table is installed. Plasma treatment of the surface of the first layer with a gas containing an element and at least one diluent gas selected from hydrogen, argon, and helium;

 As a fifth step, there is a step of decomposing at least a source gas with a high-frequency power, and laminating a layer made of a non-single crystal material as a second layer on the first layer. A method for producing a photographic photoreceptor. '

2. In the first step, an upper blocking layer containing at least silicon and one group 13 element of the periodic table is formed on the surface side of the first layer from the photoconductive layer. The method for producing a negatively charged electrophotographic photosensitive member according to claim 1, further comprising the step of:

3. The first step includes a step of forming a protective layer made of a non-single-crystal material containing at least silicon on the outermost surface of the first layer in the previous period. A method for producing the negatively charged electrophotographic photosensitive member as described. '

 4. The step of forming the upper blocking layer, the protective layer, and the second layer included in the first layer is a step of forming a layer made of a non-single-crystal material containing at least carbon and silicon. The method for producing a negatively charged electrophotographic photosensitive member according to any one of claims 2 to 3, wherein the negatively charged electrophotographic photosensitive member is provided.

 5. The step of forming the upper blocking layer is characterized in that the flow rate of the source gas is changed in order to increase the composition ratio of carbon to silicon constituting the upper blocking layer toward the surface side. A process for producing an electrophotographic photoreceptor for negative charging as described in 1.

 6. The step of forming the second layer is a step of forming a layer made of a non-single crystal material having a carbon atom as a base material. The method for producing a negatively charged electrophotographic photosensitive member according to item 2.

 7. The step of forming the upper blocking layer has a content of at least one group 13 element of the periodic table of 100 atomic ppm or more and 30000 atomic ppm or less with respect to the total number of constituent elements included in the upper blocking layer. 7. The method for producing a negatively chargeable electrophotographic photosensitive member according to claim 2, wherein the raw material gas flow rate is such a step. .

8. In the fourth step, the content of at least one group 13 element in the periodic table in the total gas flow introduced is 2.0 と す る 1θ ηο1% or more and 2.0 Χl (T ² mol% or less). The method for producing a negatively charged electrophotographic photosensitive member according to any one of claims 1 to 7, wherein:

9. The gas containing at least one group 13 element of the periodic table in the fourth step is a B ₂ H ₆ gas. The method for producing a negatively charged electrophotographic photosensitive member according to any one of the preceding claims.

 10. The process according to any one of claims 1 to 9, wherein in the third step, the process of removing at least the top of the protrusion on the surface of the first layer is a polishing process. 2. A process for producing an electrophotographic photosensitive member for a negative belt according to item 1.

 11. In the third step, before the process proceeds to the fourth step, a treatment for bringing the surface of the first layer into contact with water is performed. The method for producing a negatively chargeable electrophotographic photosensitive member according to the item.

 1 2. A photoconductive layer made of at least a non-single crystal material and a top blocking layer and a protective layer made of a non-single crystal material containing carbon and silicon on a cylindrical substrate having at least a conductive surface. An electrophotographic photosensitive member in which a first layer including a second layer made of at least a non-single crystal material is stacked on the first layer, wherein the abnormally grown portion in the first layer is the second layer. A negatively charged electrophotographic photosensitive member characterized in that the content distribution of the Group 13 element of the periodic table has a peak in the interface region between the first layer and the second layer.

 13. The negatively chargeable electrophotographic photosensitive member according to claim 12, wherein the composition ratio of carbon to silicon constituting the upper blocking layer increases toward the surface side.

14.The peak of the content distribution of Group 13 element of the periodic table in the interface region between the first layer and the second layer is 5.0 × 10 ¹⁷ pieces / cm ³ or more, 1.0 × 10 ²¹ pieces / cm ³ The electrophotographic photoreceptor for negative charging according to claim 12 or 13, wherein:

15. An electrophotographic apparatus using the negatively charged electrophotographic photosensitive member according to any one of claims 12 to 14.

16. The electrophotographic apparatus according to claim 15, wherein the charging means of the electrophotographic apparatus comprises contact charging means.